• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A process for the preparation of a fluorinated and sulfur-containing compound of the formula F-SO-R (I) or F-SO 2 -R (II) comprising the reaction, in the presence of water, of at least one salt providing a fluoride anion and at least one halosulfoxide compound of formula X-SO-R '(I0) respectively of a halosulfonyl compound of formula X-SO2-R' (II0), where X is a halogen atom different from fluorine and R and R 'are each a group covalently bonded to the sulfur atom, said bond linking said sulfur atom with a carbon atom or a nitrogen atom. Also described is a process for the preparation of said salts of a fluorinated and sulfurized compound of the formula F-SO-R (I) or F-SO2-R (II), which are advantageously used as electrolyte salts, as precursors of anti-static agent or as surfactant precursors.
    公开号:FR3014438A1
    申请号:FR1362136
    申请日:2013-12-05
    公开日:2015-06-12
    发明作者:Olivier Buisine；Francois Metz
    申请人:Rhodia Operations SAS；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the field of the preparation of fluorinated and sulfur-containing compounds in an aqueous medium and the preparation of the salts of said compounds, which are useful in applications such as those described in US Pat. than electronics and electrochromism. More particularly, the present invention relates to the preparation of bis-fluorosulfonylimide acid (FSIH) salts, especially lithium bis-fluorosulfonylimide (LiFSI).
    [0002] The production of FISH and LiFSI is widely described in the literature. Among the various technologies described, the majority implements a fluorination reaction either by HF or by metal fluorides. The use of metal fluorides is problematic because it is often not very effective and uses expensive reagents such as fluorosulphuric acid. For example, the fluorination of potassium fluoride in nitromethane or other polar organic solvents is inefficient in terms of yield (WO 2002/053494). Other technologies have been developed, for example by using chlorosulfonyl isocyanate in the presence of oleum and ammonium fluoride (JP 2012-162470) or by using urea and fluorosulfonic acid, but these technologies suffer from the strong corrosion of the medium as well as from the exothermic reaction. These disadvantages make these technologies unsuitable for industrial production of bis-fluorosulfonylimide acid and its salts.
    [0003] Also the need to produce bis-fluorosulfonylimide acid (FSIH) and more generally fluorinated and sulfur compounds and their salts by an alternative method overcoming the drawbacks mentioned above is large. Surprisingly, the Applicant has developed a new process for the production of fluorinated and sulfur compounds and their salts operating under mild conditions and without exotherm. The process according to the present invention has the advantage of being easy to implement on an industrial scale. It implements a fluorination reaction which operates in an aqueous medium. The use of water as a solvent makes it possible not only to improve the performance of the fluorination reaction in comparison with those obtained by carrying out a fluorination reaction carried out in an anhydrous medium but also to easily separate the fluorinated compound and formed sulfur, generally in salified form, of the fluorination medium.
    [0004] The present invention relates to a process for preparing a fluorinated and sulfur-containing compound of formula F-SO-R (I) or F-SO 2 -R (11) comprising the reaction, in the presence of water, of at least a salt providing a fluoride anion and at least one halosulfoxide compound of formula X-SO-R '(10) respectively of a halosulfonyl compound of formula X-SO 2 -R' (110), where X is an atom of halogen other than fluorine and R and R 'are each a group covalently bonded to the sulfur atom, said bond linking said sulfur atom with a carbon atom or a nitrogen atom.
    [0005] The process of the invention carries out a fluorination reaction or a halogen / fluorine exchange reaction, the halogen atom (s) different from the fluorine being exchanged for fluorine. The reaction scheme of the process of the invention is given below to facilitate comprehension without, however, relating the scope of the invention to this one.
    [0006] X-SO-R '+ MF -> F-SO-R + MX or X-S02-R' + MF -> F-S02-R + MX In the equations above, M is the cation associated with the fluoride anion. The groups R and R 'are identical when R' has no halogen atom other than fluorine likely to be affected by said fluorination reaction according to the method of the invention. R and R 'are different and differ from each other in the nature of the halogen when R' has one or more halogen atoms, other than fluorine, affected by said fluorination reaction. More preferably, the process of the invention relates to the preparation of said fluorinated and sulfurized compound of formula F-SO 2 -R (11) from said halosulfonyl compound of formula X-SO 2 -R '(110). According to a first preferred embodiment of the process of the invention, the group R is a group -NHSO2F, a group -NM'SO2F (M 'being an alkaline or alkaline earth metal), a group -NRi R10, a group - NHSO2Ri, a group -NHCORi where R1 and R10, identical or different, are selected from the group consisting of a hydrogen atom, a linear hydrocarbon chain, branched or cyclic, saturated or unsaturated having from 1 to 15 carbon atoms, a fluoroalkyl, perfluoroalkyl or fluoroalkenyl chain having 1 to 15 carbon atoms and an aromatic group. The aromatic group covers in particular a monocyclic or polycyclic aryl or heteroaryl radical, the aryl radical being preferably a 5- to 6-membered aromatic ring. Said aryl or heteroaryl radical may itself carry one or more substituents, for example a linear or branched, saturated or unsaturated carbon chain, a halogen, hydroxy, trifluoromethyl, trifluoromethoxy, methoxy, carboxy, amine or oxo group, nitro or cyano. Very advantageously, the group R is a group -NHSO2F, a group -NM'SO2F (M 'being an alkali or alkaline earth metal) or a group -NHSO2R1 where R1 is a fluoroalkyl or perfluoroalkyl chain, preferentially a perfluoroalkyl chain having 1 to 5 carbon atoms, very preferably R 1 is the group -CF 3.
    [0007] According to said first preferred embodiment, the group R 'is a group -NHSO2X (X having the definition given above), a group - NR'iR'10, a group -NHSO2R'1, a group -NHCOR'1 where R'1 and R'10, which are identical or different, are chosen from the group consisting of a hydrogen atom, a linear, branched or cyclic hydrocarbon chain, saturated or unsaturated having from 1 to 15 carbon atoms, a haloalkyl chain; , perhaloalkyl or haloalkenyl wherein the halogen atom (s) is (are) selected from bromine, chlorine, fluorine and iodine and having from 1 to 15 carbon atoms and a group aromatic. Very advantageously, the group R 'is a group -NHSO2X (X having the definition given above, preferably X is chlorine) or a group -NHSO2R'1 where R'1 is a haloalkyl or perhaloalkyl chain. Said first preferred embodiment is particularly advantageous when the fluorination reaction is carried out in the presence of said halosulfonyl compound of formula X-502-R '(110) to prepare said fluorinated and sulfur-containing compound of formula F-502-R (II). In a very preferred manner and according to said first embodiment, the method of the invention is carried out using a halosulfonyl compound of formula (110) X-502-NH-502-X (X having the definition given above). , preferably X is chlorine) so as to prepare the compound F-502-NH-502-F (II), called bis-fluorosulfonylimide acid (FSIH) or a salt of said compound (F-502-NM'-502-F where M 'is an alkaline or alkaline earth metal). It is also possible to employ a metal or organic salt of said halosulfonyl compound of formula (110). Also very preferably, and according to said first embodiment, the method of the invention is carried out using a halosulfonyl compound of formula (110) X-SO2-NH-SO2-CF3 (X having the definition given below. above, preferably X is chlorine) so as to prepare the compound F-SO2-NH-SO2-CF3 (II). According to a second preferred embodiment of the process of the invention, the group R is an alkyl hydrocarbon chain, a fluoroalkyl, perfluoroalkyl or fluoroalkenyl chain, an aromatic group, an alkenyl group or a nitrile group. Said alkyl chains and said aromatic and alkenyl groups may be substituted. The term "alkyl" especially covers a linear, branched or cyclic carbon chain, saturated, which may contain one or more heteroatoms (N, O, S), which may contain one or more unsaturations, and which may contain one or more substituents, unless otherwise indicated. . Preferably, such a linear or branched chain comprises from 1 to 15 carbon atoms, and preferably from 1 to 2 to 10 carbon atoms. The term "aromatic" especially covers a monocyclic or polycyclic aryl or heteroaryl radical comprising carbon and hydrogen atoms. The aryl or heteroaryl radical is preferably a 5- to 6-membered aromatic ring comprising, for example, 1, 2, 3, 4, or 5 heteroatoms chosen in particular from nitrogen, sulfur and oxygen. The aryl or heteroaryl radicals may themselves carry one or more substituents, for example chosen from the halogen, hydroxy, trifluoromethyl, trifluoromethoxy, methoxy, carboxy, amine, oxo, nitro or cyano group. Examples of aromatic groups include, but are not limited to, phenyl, tolyl, anthracenyl, fluorenyl, indenyl, azulenyl, and naphthyl, benzo-fused carbocyclic radicals such as 5,6,7,8-tetrahydronaphthyl. An aromatic group may be substituted with one or more substituents or unsubstituted. According to one variant, the aromatic group is a monocyclic ring with 6 carbon atoms. The alkenyl group is typically a hydrocarbon group comprising in the alpha position of the sulfur atom of the formula (I) or the formula (II) an unsaturation (C = C).
    [0008] According to the process according to the invention, the nature of said salt providing at least said fluoride anion may be of varied nature. Advantageously, said salt is chosen from metal fluorides, onium fluorides and mixtures thereof.
    [0009] Said metal fluorides, advantageously employed as salts providing fluoride anions in the process according to the invention, are preferably fluorides in which the metal cations belong to groups IA, IIA and IIB of the periodic table of the elements. As examples of suitable cations for carrying out the process of the invention, mention may be made more particularly of the cations of group IA, lithium, sodium, potassium and cesium, among the cations of group IIA. , magnesium and calcium, and among group IIB cations, zinc. Among the above-mentioned salts, potassium fluoride and sodium fluoride are preferably chosen. The invention does not exclude the use of double salts such as double fluorides of aluminum and sodium or potassium and sodium or potassium fluosilicates.
    [0010] Said onium fluorides, advantageously employed as salts providing fluoride anions in the process according to the invention, are preferably chosen from ammonium fluorides, phosphonium fluorides, imidazolium fluorides, guanidinium fluorides and fluorides. pyridinium, taken alone or as a mixture.
    [0011] Ammonium fluorides and phosphonium fluorides are salts whose cation corresponds in particular to the following formula (III): in which: - W represents N or P, - R2, R3, R4, and R5, which are identical or different; represent:. a linear or branched alkyl group having 1 to 16 carbon atoms and optionally substituted by one or more heteroatoms or phenyl, hydroxyl, halogen, nitro, alkoxy or alkoxycarbonyl groups, the alkoxy groups having 1 to 4 carbon atoms; . a linear or branched alkenyl group having 2 to 12 carbon atoms; . an aryl group having 6 to 10 carbon atoms, optionally substituted by one or more heteroatoms or alkyl groups having 1 to 4 carbon atoms, alkoxy, alkoxycarbonyl, alkoxy group having 1 to 4 carbon atoms, or halogen.
    [0012] Ammonium fluorides and phosphonium fluorides, preferably used for carrying out the process according to the invention, have a cation which corresponds to formula (III) in which W is a nitrogen or phosphorus atom and R 2 R3, R4 and R5, which may be identical or different, are chosen from a linear or branched alkyl group having 1 to 4 carbon atoms and a benzyl group. By way of more specific examples, mention may be made of tetrabutylammonium, methyltri (n-butyl) ammonium, N-methyl-N, N, N-trioctylammonium, trimethylphenylphosphonium, tetrabutylphosphonium, methyltri (n-butyl) phosphonium fluorides. , methyltri (isobutyl) phosphonium, diisobutyl-n-octylmethylphosphonium. Tetrabutylammonium fluoride (R 2 = R 3 = R 4 = R 5 = butyl and W = N) and tetrabutylphosphonium fluoride (R 2 = R 3 = R 4 = R 5 = butyl and W = P) are preferably selected. Imidazolium fluorides and pyridinium fluorides are salts providing fluoride anions and whose cation respectively corresponds to formula (IV) or formula (V) below: ## STR2 ## in which: R 6 represents an alkyl group having 1 to 20 carbon atoms, R 7 represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms; - the group R8 represents an alkyl group having from 1 to 4 carbon atoms; - the group R9 represents an alkyl group having from 1 to 6 carbon atoms. Among the cations corresponding to formulas (IV) and (V), the cations 1-alkyl-2,3-dimethylimidazolium (R 6 = C 1 -C 20 alkyl, R 7 = R 8 = methyl), 1-alkyl-3-methylimidazolium (R 6 = C 1 -C 20 alkyl, R 7 = H, R 8 = methyl) and 1-alkylpyridinium (R 9 = C 1 -C 6 alkyl) are preferred. More specific examples of imidazolium fluorides include 1-alkyl-2,3-dimethylimidazolium fluorides such as 1-ethyl-2,3-dimethylimidazolium fluoride, 1-butyl-2,3-dimethylimidazolium fluoride. 1-hexy1-2,3-dimethylimidazolium; 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-hexy-2,3-dimethylimidazolium; 1-alkyl-3-methylimidazolium fluorides, such as 1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium fluoride, 1-octyl-3-methylimidazolium fluoride, 1-decyl-3-methylimidazolium fluoride, 1-dodecyl-3-methylimidazolium, 1-tetradecyl-3-methylimidazolium, 1-hexadecyl-3-methylimidazolium, 1-octadecyl-3-methylimidazolium; 1-butyl-3-methylimidazolium hexafluorophosphate, 1-hexy-3-methylimidazolium, 1-octyl-3-methylimidazolium hexafluorophosphate; 1-butyl-3-methylimidazolium tetrafluoroborate, 1-hexy-3-methylimidazolium. The preferred imidazolium fluorides are 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium tetrafluoroborate. As more specific examples of pyridinium fluorides, mention may be made of 1-alkylpyridinium salts such as 1-ethylpyridinium, 1-butylpyridinium, 1-hexylpyridinium fluoride; 1-butylpyridinium hexafluorophosphate, 1-hexylpyridinium; 1-butylpyridinium tetrafluoroborate, 1-hexylpyridinium. Said halosulfoxide compound of formula (10) or said halosulfonyl compound of formula (110) used as reagent for carrying out the process according to the invention is in acid form or in salified form. Salified form is advantageously used salts of alkali and alkaline earth metals or organic salts in the form of ionic liquid, especially onium salts and more particularly ammonium salts (very preferably a tetrabutylammonium salt) , phosphonium, imidazolium, pyridinium, guanidinium.
    [0013] According to the process of the invention, the fluorination reaction is carried out between said compound of formula (10) or said compound of formula (110) and the salt bringing the fluoride anion in the presence of water. The amount of said salt in water is such that it represents 1% by weight, preferably 10% by weight until saturation of the water at the reaction temperature. The reaction may also be carried out in a hydro-organic medium, in particular using a polar or apolar organic solvent.
    [0014] The fluorination reaction is advantageously carried out at a temperature of between 20 and 160 ° C, preferably between 60 and 120 ° C. It is advantageously conducted under atmospheric pressure. It is conducted for a period preferably between a few minutes and 20 hours, very preferably between 0.5 and 10 hours. According to the process of the invention, the molar ratio between the number of moles of said halosulfoxide compound or said halosulfoyl compound and the number of moles of salt expressed as fluoride anion is between 1 and 20 and preferably between 3 and 10. In accordance with method of the invention, the fluorination reaction is conducted in a monophasic or two-phase liquid / liquid medium.
    [0015] The method of the invention is simple to implement. The reagents can be introduced in any order according to different variants but some are preferred. A preferred embodiment comprises introducing said compound of formula (10) or (110) onto a mixture of water and said salt providing at least said fluoride anion. The addition of said compound of formula (10) or (110) is preferably carried out once said aqueous mixture has been heated to a temperature within the aforementioned range. The fluorinated and sulfurized compound of formula (I) or (11) obtained at the end of the implementation of said fluorination reaction is in the form of a neutral molecule or in salified form. The salified form is obtained when said halosulfoxide compound or said halosulfonyl compound has an acidic hydrogen whose pKa in water is less than 7. Preferably, said fluorinated and sulfurized compound of formula (I) or (11) is obtained. salified form. For example, in the implementation of the preferred embodiment of the process according to the invention consisting in using bis-chlorosulfonylimide acid or one of its salts as a compound of formula (110), at the end of the implementation of said fluorination reaction a salt of bis-fluorosulfonylimide acid, for example a potassium salt (potassium bis-fluorosulfonylimide) when said salt providing said fluoride anion is potassium fluoride.
    [0016] The process for preparing said fluorinated and sulfur-containing compound according to the invention is advantageously carried out in an apparatus capable of withstanding the corrosion of the reaction medium.
    [0017] For this purpose, materials are chosen for the part in contact with the corrosion-resistant reaction medium such as alloys based on molybdenum, chromium, cobalt, iron, copper manganese, titanium, zirconium, aluminum, carbon and tungsten sold under the HASTELLOY® brands or alloys of nickel, chromium, iron, manganese with added copper and / or molybdenum sold under the name INCONEL®, MONELTM and more particularly alloys HASTELLOY C 276 or INCONEL 600, 625 or 718. It is also possible to choose stainless steels, such as austenitic steels [Robert H. Perry et al., Perry's Chemical Engineers' Handbook, Sixth Edition (1984), page 23-44] and more particularly 304, 304 L, 316 or 316 L stainless steels. uses a steel having a nickel content at most 22% by weight, preferably between 6 and 20%, and more preferably between 8 and 14%. The 304 and 304 L steels have a nickel content ranging between 8 and 12% and the 316 and 316 L steels have a nickel content ranging between 10 and 14%. 316 L steels are more particularly chosen. It is also possible to use an apparatus consisting of or coated with a polymeric compound that is resistant to corrosion of the reaction medium. Mention may in particular be made of materials such as PTFE (polytetrafluoroethylene or Teflon) or PFA (perfluoroalkyl resins). It will not be departing from the scope of the invention to use an equivalent material. As other materials that may be suitable for being in contact with the reaction medium, mention may also be made of graphite derivatives. When the fluorinated and sulfurized compound of formula (I) or (II) obtained at the end of the implementation of said fluorination reaction is immiscible in the reaction medium, in particular when it is a neutral molecule or a salt of said immiscible compound in the reaction medium, for example an onium salt, said compound is isolated, purified, optionally converted according to conventional techniques known to those skilled in the art.
    [0018] The present invention also relates to a process for the preparation of at least one salt of said fluorinated and sulfurized compound of formula (I) or (II) from the process for the preparation of said compound of formula (I) or (II) such that described above. Said salt of said fluorinated and sulfur-containing compound of formula (I) or (II) is preferably an alkali metal salt (Li, Na, K, Rb, Cs), a salt of an alkaline earth metal, a salt of a transition metal or a salt selected from lanthanides. Preferably, it is a salt of an alkali metal, very preferably a lithium salt. In particular, when said fluorinated and sulfur-containing compound of formula (I) or (II) is a bis-fluorosulfonylimide acid salt, lithium bis-fluorosulfonylimide (LiFSI) is advantageously prepared. The process for preparing at least one salt of said fluorinated and sulfurized compound of formula (I) or (II) according to the invention comprises the preparation of said compound of formula (I) or (II) in salified form according to the method described herein. above followed by a liquid / liquid extraction step and the implementation of either a sequence comprising the steps of acidification, recovery of the acid obtained and neutralization or a reaction of exchange of cations.
    [0019] The process for the preparation of at least said salt of said fluorinated and sulfurized compound of formula (I) or (II) according to the invention is suitable when said compound of formula (I) or (II) obtained at the end of said reaction fluorination is in the form of a miscible salt in the aqueous reaction medium. Said reaction medium is subjected to a liquid / liquid extraction step so as to extract said salt of said compound of formula (I) or (II) obtained at the end of said fluorination reaction. More specifically, said reaction medium is brought into contact with an onium salt leading to the formation of an organic phase comprising the complex resulting from the reaction of said miscible salt of said compound of formula (I) or (II) obtained with the result of said fluorination reaction with the onium salt and an aqueous phase comprising the various salts, in particular that resulting from the reaction of the cation of said miscible salt with the anion of onium. Said onium salt advantageously employed for carrying out the liquid / liquid extraction is preferably chosen from ammonium salts, phosphonium salts, imidazolium salts, guanidinium salts and pyridinium salts, taken alone or mixed. The formulas of these salts have been specified above in the present description. Said liquid / liquid extraction step is carried out in the presence of an organic solvent, preferably a halogenated organic solvent, for example dichloromethane or dichloroethane. It is conducted at a temperature between 10 and 100 ° C, preferably between 20 and 40 ° C. Said liquid / liquid extraction step has already been described in patent application FR 2,933,693.
    [0020] Said complex obtained is present in the organic phase and the aqueous and organic phases are separated, in particular by decantation, so as to recover an ionic liquid of said compound of formula (I) or (II).
    [0021] According to a first embodiment of the process for the preparation of said salt of said fluorinated and sulfurized compound of formula (I) or (II) according to the invention, the said complex obtained is acidified in the said organic phase so as to release the same. acid function. Said acidification step is carried out by means of a treatment with a strong Briinstedt acid, for example sulfuric acid, hydrochloric acid, phosphoric acid, sulphonic acid or acid. nitric. The proton stoichiometry provided by the acid relative to said complex varies from 1 to 10 molar equivalents, preferably from 1 to 4 molar equivalents. The acidification is preferably carried out at a temperature between 10 and 50 ° C. At the end of said acidification step, said compound of formula (I) or (II) is in acid form in the organic phase. It is recovered according to standard techniques known to those skilled in the art, in particular by distillation or by extraction. Said compound of formula (I) or (II) in acid form is very preferably recovered by distillation. The organic solvent used for carrying out the liquid / liquid extraction step, prior to the decantation step, is first distilled at atmospheric pressure, and then said compound of formula (I) or (II) under acid form is distilled under reduced pressure.
    [0022] The implementation of said distillation step is advantageous because it makes it possible to reach said compound with the high purity required for electronic applications. Said compound of formula (I) or (II) in acid form thus obtained in purified form is dissolved in an organic solvent to be subjected to a neutralization step. Said organic solvent is preferably a chlorinated aliphatic solvent or an aromatic solvent. In particular, it is dichloromethane or dichloroethane. The neutralization is carried out by treatment with a metal hydroxide, a metal chloride or a metal hydride, the metal cation associated with the hydroxide anion being a monovalent or divalent cation, preferably the lithium cation. Preferably, the neutralization is carried out in the presence of lithium hydroxide or lithium chloride. The neutralization is conducted at a temperature between 10 and 100 ° C, preferably between 10 and 40 ° C. Said neutralization step is easy to implement. Advantageously, said compound of formula (I) or (II) in acid form obtained after distillation is dissolved in an organic solvent and then an aqueous solution of hydroxide, chloride or metal hydride is added. The organic and aqueous phases are separated by decantation or filtration and the organic phase is evaporated. The salt of said fluorinated and sulfur-containing compound of formula (I) or (II) is advantageously recovered from the aqueous phase. According to a second embodiment of the method for preparing said salt of said fluorinated and sulfurized compound of formula (I) or (II) according to the invention, a cation exchange reaction is carried out on the complex obtained after said decantation step. explained above in the present description. Said cation exchange reaction is carried out by contacting the organic phase comprising said complex with an aqueous solution of metal hydroxide or metal halide, the metal cation associated with the hydroxide or halide anion being monovalent or divalent . Preferably, said metal hydroxide is lithium hydroxide. The stoichiometry in metal cation with respect to said complex is between 0.5 and 5 molar equivalents, preferably between 1 and 2. Said exchange reaction is carried out at a temperature of between 10 and 100 ° C., preferably between 10 and 10 ° C. 40 ° C. At the end of the reaction, the organic and aqueous phases are separated by decantation. The organic phase is evaporated and said salt of said fluorinated and sulfurized compound of formula (I) or (II) obtained from the aqueous phase is preferably dried under vacuum.
    [0023] Another subject of the present invention is the use of said fluorinated and sulfur-containing compound of formula F-SO-R (I) or F-502-R (II) or a salt of said fluorinated and sulfur-containing compound of formula (I) or (II) prepared according to the methods described above as electrolyte salts, as antistatic agent precursors or as surfactant precursors. In particular, said compound of formula (I) or (II) or its salts are advantageously used as electrolytes for the manufacture of batteries, in the field of electrochromism and electronics. They are advantageously used as antistatic agents for the manufacture of pressure sensitive adhesives (PSA). As an anti-static agent, they can still be used as lubricant components. They are used in optical materials such as electroluminescent devices and are used in the composition of photovoltaic panels.
    [0024] Examples of embodiments of the invention are given below. These examples are given for illustrative purposes and without limitation.
    [0025] Examples 1 to 5: In a glass reactor, a solution of potassium fluoride in aqueous solution is brought to the reaction temperature. Bis-chlorosulfonylimide, CSIH (10 grams, 47 mmol) is added over 30 seconds and stirring is continued for 2 hours at the reaction temperature. The reaction medium is diluted with water for analysis carried out by 19 F NMR in order to calculate the yield of potassium bis-fluorosulfonylimide (FSIK).
    [0026] The following table gathers the operating conditions used and the results obtained: Stoichiometry KF Example No. (equivalents) Molar ratio H20 / KF Temperature (° C) Conversion CSIH (%) Yield FSIK (%) 1 10 2.8 100 100% 38 % 2 10 2.7 75 100% 51% 3 10 2.3 50 100% 65% 4 15 2.4 50 100% 60% 5 20.8 2.5 50 100% 65% Comparative Example: Fluoride fluoridation zinc in an organic medium Zinc fluoride (5.1 g, 49 mmol) is dissolved in 90 g of valeronitrile. The bis-chlorosulfonylimide is then added and stirring is maintained for 24 hours at room temperature. NMR analysis shows a conversion of bis-chlorosulfonylimide of 100%, and the yield of zinc salt of bis-fluorosulfonylimide is 12%.
    权利要求:
    Claims (12)
    [0001]
    REVENDICATIONS1. Process for preparing a fluorinated and sulfur-containing compound of formula F-SO-R (I) or F-502-R (11) comprising reacting, in the presence of water, at least one salt providing a fluoride anion and at least one halosulfoxide compound of formula X-SO-R '(10) or a halosulfonyl compound of formula X-502-R' (110), respectively, where X is a halogen atom different from fluorine and R and R 'are each a group covalently bonded to the sulfur atom, said bond linking said sulfur atom with a carbon atom or a nitrogen atom.
    [0002]
    2. Process for the preparation of a fluorinated and sulfur-containing compound of formula F-SO-R (I) or F-502-R (11) according to claim 1, in which the group R is a group -NHSO2F, a group-NM SO2F (M 'being an alkali or alkaline earth metal), a group -NRi R10, a group -NHSO2R1, a group -NHCORi where R1 and R10, identical or different, are chosen from the group consisting of an atom of hydrogen, a linear, branched or cyclic, saturated or unsaturated hydrocarbon chain having 1 to 15 carbon atoms, a fluoroalkyl, perfluoroalkyl or fluoroalkenyl chain having 1 to 15 carbon atoms and an aromatic group.
    [0003]
    A process for preparing a fluorinated and sulfurized compound of the formula F-SO-R (I) or F-502-R (11) according to claim 1 or claim 2, wherein a halosulfonyl compound of the formula (110) is used. ) X-502-NH-502-X so as to prepare the compound F-502-NH-502-F (11).
    [0004]
    A process for preparing a fluorinated and sulfurized compound of the formula F-SO-R (I) or F-502-R (11) according to claim 1 or claim 2, wherein a halosulfonyl compound of the formula (110) is used. ) X-502-NH-502-CF3 to prepare the compound F-502-NH-502-CF3 (11).
    [0005]
    5. Process for the preparation of a fluorinated and sulfur-containing compound of formula F-SO-R (I) or F-502-R (11) according to claim 1, in which the group R is an alkyl hydrocarbon chain, a fluoroalkyl chain, perfluoroalkyl or fluoroalkenyl, an aromatic group, an alkenyl group or a nitrile group.
    [0006]
    6. Process for preparing a fluorinated and sulfur-containing compound of formula F-SO-R (I) or F-SO 2 -R (11) according to one of claims 1 to 5 wherein said salt providing a fluoride anion is chosen among metal fluorides, onium fluorides and mixtures thereof.
    [0007]
    7. Process for the preparation of a fluorinated and sulfur-containing compound of formula F-SO-R (I) or F-SO 2 -R (11) according to one of claims 1 to 6 wherein said halosulfoxide compound of formula (10) or said halosulfonyl compound of formula (110) is in acid form or in salified form.
    [0008]
    8. Process for preparing a fluorinated and sulfur-containing compound of formula F-SO-R (I) or F-SO 2 -R (11) according to one of claims 1 to 7 wherein said fluorinated and sulfur-containing compound is obtained. formula F-SO-R (I) or F-S02-R (11) in salified form.
    [0009]
    9. A process for preparing at least one salt of said fluorinated and sulfur-containing compound of formula (I) or (11) comprising the preparation of said compound of formula (I) or (II) in salified form according to the process as defined in US Pat. Claims 1 to 8 followed by a liquid / liquid extraction step and then the implementation of a sequence comprising the acidification, recovery of the acid obtained and neutralization steps, or a reaction of cation exchange.
    [0010]
    A process for preparing at least one salt of said fluorinated and sulfurized compound of formula (I) or (11) according to claim 9 wherein said salt of said fluorinated and sulfurized compound of formula (I) or (11) is a salt. an alkali metal (Li, Na, K, Rb, Cs), a salt of an alkaline earth metal, a salt of a transition metal or a salt selected from lanthanides.
    [0011]
    11. Process for the preparation of at least one salt of said fluorinated and sulfur-containing compound of formula (I) or (11) according to claim 9 or claim 10 in which the lithium bis-fluorosulfonylimide (LiFSI) is prepared.
    [0012]
    12. Use of the fluorinated and sulfur-containing compound of formula F-SO-R (I) or F-SO 2 -R (II) prepared according to the process as defined according to one of claims 1 to 8 or a salt of said compound fluorinated and sulfur-containing compound of formula F-SO-R (I) or F-SO 2 -R (II) prepared according to one of claims 9 to 11 as electrolyte salts, as antistatic agent precursors or as surfactant precursors. -active.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP3077333B1|2019-02-20|Method for producing a fluorine- and sulphur-bearing compound and salts thereof in an aqueous medium
    EP3077334B1|2019-08-21|Method for preparing bis|imide acid and salts thereof
    KR102300703B1|2021-09-09|Solvent-free alkane sulfonation
    US8653302B2|2014-02-18|Processes for preparing poly|aromatic compounds
    US20150246812A1|2015-09-03|Method for preparing imide salts containing a fluorosulphonyl group
    EP2714663A1|2014-04-09|Method for preparing a fluorinated organic compound
    FR2933693A1|2010-01-15|PROCESS FOR SEPARATING CARBOXYLIC ACID IN SALIENT FORM CARRIER OF AT LEAST ONE HALOGEN ATOM
    US8937204B1|2015-01-20|Processes for isolating fluorinated products
    WO2012120067A1|2012-09-13|Method for preparing difluoroacetonitrile and the derivatives thereof
    CA2931997C|2022-03-01|Method for producing a fluorine- and sulphur-bearing compound and salts thereof in an aqueous medium
    WO2009144281A1|2009-12-03|Method for the sulphonylation of a hydroxylated organic compound
    FR2932178A1|2009-12-11|PROCESS FOR HYDROXYLATION OF PHENOLS AND PHENOL ETHERS
    WO2012016881A1|2012-02-09|Process for preparing difluoroacetic acid, salts thereof or esters thereof
    WO2012163896A1|2012-12-06|Method for the preparation of a fluoro-methylpyrazole compound in carboxylic acid or derivative form
    EP1517888A2|2005-03-30|Method for synthesis of hydrogenofluoromethylenesulphonyl radical derivatives
    FR2768728A1|1999-03-26|A new process for the acylation of an aromatic compound
    FR2787787A1|2000-06-30|PROCESS FOR THE PREPARATION OF DIPHENYL AROMATIC THIOETHERS
    JP2009013118A|2009-01-22|Method for producing alkane compound
    同族专利:
    公开号 | 公开日
    WO2015082519A1|2015-06-11|
    KR20160095027A|2016-08-10|
    CA2931997A1|2015-06-11|
    TWI654135B|2019-03-21|
    EP3077333B1|2019-02-20|
    FR3014438B1|2017-10-06|
    KR102351641B1|2022-01-17|
    PL3077333T3|2019-08-30|
    TW201542447A|2015-11-16|
    EP3077333A1|2016-10-12|
    CN105960377A|2016-09-21|
    US20160304347A1|2016-10-20|
    JP6527152B2|2019-06-05|
    JP2017510528A|2017-04-13|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP2660196A1|2011-03-03|2013-11-06|Nippon Soda Co., Ltd.|Manufacturing method for fluorosulfonylimide ammonium salt|
    FR2818972B1|2000-12-29|2003-03-21|Rhodia Chimie Sa|PROCESS FOR FLUORINATION OF A HALOGEN COMPOUND|
    FR2933693B1|2008-07-10|2010-09-03|Rhodia Operations|PROCESS FOR SEPARATING CARBOXYLIC ACID IN SALIENT FORM CARRIER OF AT LEAST ONE HALOGEN ATOM|
    JP5443118B2|2009-03-31|2014-03-19|三菱マテリアル株式会社|Method for producing bis imide salt, method for producing bis imide salt and fluorosulfate, and method for producing bis imide / onium salt|
    JP5527993B2|2009-03-31|2014-06-25|三菱マテリアル株式会社|Method for producing bis imide|
    KR101345271B1|2009-11-27|2013-12-27|가부시기가이샤 닛뽕쇼꾸바이|Fluorosulfony limide salt and method for producing fluorosulfonyl imide salt|
    JP2012162470A|2011-02-04|2012-08-30|Mitsubishi Materials Corp|Method of manufacturing bis amide salt and perfluoro-n- alkane sulfonyl amide salt|
    FR2975694B1|2011-05-24|2013-08-02|Arkema France|PROCESS FOR THE PREPARATION OF BIS IMIDURE OF LITHIUM|
    JP5899789B2|2011-10-18|2016-04-06|住友電気工業株式会社|Method for producing imide salt|
    US8722005B1|2013-07-26|2014-05-13|Boulder Ionics Corporation|Synthesis of hydrogen bisimide|
    FR3014439B1|2013-12-05|2018-03-23|Rhodia Operations|PROCESS FOR THE PREPARATION OF BIS-FLUOROSULFONYLIMIDE ACID AND ITS SALTS|CN105858626B|2016-03-31|2017-02-08|南京远淑医药科技有限公司|A preparing method of lithium bisimide|
    CN105967159B|2016-04-29|2018-06-01|南京远淑医药科技有限公司|A kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine|
    CN105836719B|2016-04-29|2018-06-01|南京远淑医药科技有限公司|A kind of method for synthesizing imidodisulfuryl fluoride lithium salt using fragrant methyl amine|
    CN106430257B|2016-10-09|2019-03-12|多氟多化工股份有限公司|A kind of preparation method of porous high activity lithium fluoride and the preparation method of bis-imine lithiums|
    US11267707B2|2019-04-16|2022-03-08|Honeywell International Inc|Purification of bis imide|
    CN112408337A|2020-11-14|2021-02-26|四川大学|Method for controllably producing sulfur dioxide|
    法律状态:
    2015-11-10| PLFP| Fee payment|Year of fee payment: 3 |
    2016-11-11| PLFP| Fee payment|Year of fee payment: 4 |
    2017-11-13| PLFP| Fee payment|Year of fee payment: 5 |
    2019-11-15| PLFP| Fee payment|Year of fee payment: 7 |
    2020-11-12| PLFP| Fee payment|Year of fee payment: 8 |
    2021-11-15| PLFP| Fee payment|Year of fee payment: 9 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1362136A|FR3014438B1|2013-12-05|2013-12-05|PROCESS FOR THE PREPARATION OF A FLUORINE AND SULFUR COMPOUND AND ITS SALTS IN AQUEOUS MEDIUM|FR1362136A| FR3014438B1|2013-12-05|2013-12-05|PROCESS FOR THE PREPARATION OF A FLUORINE AND SULFUR COMPOUND AND ITS SALTS IN AQUEOUS MEDIUM|
    TW103140262A| TWI654135B|2013-12-05|2014-11-20|Method for preparing fluorine-containing and sulfur-containing compounds and salts thereof in an aqueous medium|
    PL14805938T| PL3077333T3|2013-12-05|2014-12-03|Method for producing a fluorine- and sulphur-bearing compound and salts thereof in an aqueous medium|
    EP14805938.9A| EP3077333B1|2013-12-05|2014-12-03|Method for producing a fluorine- and sulphur-bearing compound and salts thereof in an aqueous medium|
    CN201480075024.1A| CN105960377A|2013-12-05|2014-12-03|Method for producing fluorine- and sulphur-bearing compound and salts thereof in aqueous medium|
    PCT/EP2014/076355| WO2015082519A1|2013-12-05|2014-12-03|Method for producing a fluorine- and sulphur-bearing compound and salts thereof in an aqueous medium|
    KR1020167017575A| KR102351641B1|2013-12-05|2014-12-03|Method for producing a fluorine- and sulphur-bearing compound and salts thereof in an aqueous medium|
    US15/101,138| US20160304347A1|2013-12-05|2014-12-03|Method for producing a fluorine-and sulphur-bearing compound and salts thereof in an aqueous medium|
    JP2016536651A| JP6527152B2|2013-12-05|2014-12-03|Process for producing fluorine-containing and sulfur-containing compounds and salts thereof in aqueous medium|
    CA2931997A| CA2931997A1|2013-12-05|2014-12-03|Method for producing a fluorine- and sulphur-bearing compound and salts thereof in an aqueous medium|
    [返回顶部]